Use of 1,4-anhydroglucitol/galactitol in low calorie food products, and a method of preparing 1,4-anhydro-dl-galactitol

ABSTRACT

Low calorie food products that contain highly crystalline bulking agents that impart improved texture and mouthfeel to the food products are described. The food products contain 1,4-anhydroglucitol or 1,4-anhydrogalactitol and a food ingredient. A method of preparing 1,4-anhydro-DL-galactitol comprising heating galactitol in a water-immiscible, high-boiling, reaction-inert medium in the presence of a mineral acid is also described.

This is a National Stage application under 35 U.S.C. §371 ofInternational Application No. PCT/IB95/00308, filed Apr. 28, 1995 whichis a continuation of U.S. Pat. application Ser. No. 08/311,087 filedSep. 23, 1994, now abandoned.

BACKGROUND ART

The field of art to which this invention is directed is food products,and in particular low calorie food products, low calorie bulking agents,and also methods of preparing low calorie bulking agents.

Many substances are used in the manufacture of foods intended forpersons who must restrict their intake of carbohydrates or calories orboth. Generally, ingredients which are to be included in these foodsmust be of low calorific value. Furthermore, the dietetic foods producedwith these ingredients must closely resemble calorie-containing foods intexture, taste and physical appearance. In addition, these ingredientsmust not, of course, present any problems of toxicity to the consumer ofthe food. Many materials which have been proposed for use in dieteticfoods do not satisfy all of these requirements simultaneously.

Where a synthetic sweetener such as saccharin or cyclamate is used in adietetic food to replace the sugar present in the natural food, theother physical properties, aside from sweetness, which were imparted tothe natural food by the sugar must be imparted to the synthetic dieteticfood by additional ingredients other than the synthetic sweetener. Someof the additional ingredients suggested for this use are nutritivethemselves, and therefore add undesirable calorific value to the food toreplace the calorific value contained in the sugar which was removed.Some of these ingredients may also alter the texture or eating qualitiesof the food so that it becomes unappealing or unwholesome. Finally,these additional ingredients may impart an unnatural color to the food,and, consequently, render it less palatable.

One low calorie food ingredient that has met with acceptance ispolydextrose. Polydextrose is a low-calorie food ingredient typicallyused as a bulking agent to replace higher caloric food ingredients(e.g., sugars, fats) in food compositions. In general, polydextrose is arandomly bonded condensation polymer of dextrose and polycarboxylicacids (e.g., citric acid). There are a variety of polydextroses andthese different polydextrose modifications can have different propertiesas food additives.

Polyols such as sorbitol (D-glucitol) and mannitol have widespreadcommercial application and are commonly used food ingredients. As agroup the acyclic polyols are crystalline bodies covering a wide rangein melting point and in taste ranging from faintly sweet to very sweet.The polyols commonly used in foods range in caloric availability fromessentially fully caloric (sorbitol) to ca. 50% caloric (mannitol,lactitol). By removal of the elements of water from polyols it ispossible to generate a number of cyclic anhydrides, or anhydropolyols.

Dulcitan, which consists mainly of 1,4-anhydrogalactitol is known to benon-metabolizable (Advances in Carbohydrate Chemistry 1, 175 (1945)). Atleast two other anhydrohexitols (1,4-anhydromannitol and1,5-anhydro-D-sorbitol) are also said to be nonmetabolizable.

Although such food additives as polydextrose make a significant advancein the field of food products there is a continual search foralternative low-calorie food bulking agents that impart the desiredcharacteristics to food compositions, particularly the combination oflow caloric utilization and crystallinity.

SUMMARY OF THE INVENTION

This invention is directed to a low calorie food product that contains alow calorie bulking agent that imparts improved taste qualities to thefood product. The food product comprises 1,4-anhydroglucitol or1,4-anhydrogalactitol and a food ingredient. Particularly preferredbulking agents include 1,4-anhydro-D-glucitol or 1,4-anhydro-DL-galactitol.

Another aspect of this invention is a method of preparing1,4-anhydro-DL-galactitol comprising heating galactitol in awater-immiscible, reaction-inert medium that has a boiling point ofabout 175° C. to about 225° C. in the presence of a mineral acid. Aparticularly preferred mineral acid is phosphoric acid and aparticularly preferred medium is undecane.

Yet another aspect of this invention is the novel bulking agent1,4-anhydro-L-glucitol.

These low calorie food products make a significant advance in the fieldof food products by providing reduced calorie, highly crystalline,bulking agents that have improved texture and mouthfeel.

Other features and advantages will be apparent from the specificationand claims.

DETAILED DESCRIPTION OF THE INVENTION

1,4-Anhydro-D-glucitol may be prepared using the procedure disclosed inActa Chem. Scand., B35, 441-449 (1981), whereby D-sorbitol is heatedwith an aqueous mineral acid such as sulfuric acid. The L-enantiomer,1,4-anhydro-L-glucitol, may be prepared from L-glucitol by an analogousprocedure. L-glucitol may be prepared by sodium borohydride reduction ofL-glucose. The D and L enantiomers may simply be combined to form a1,4-anhydro-DL-glucitol mixture.

1,4,-Anhydro-DL-galactitol may be prepared by heating galactitol (i.e.,meso-galactitol), preferably at a temperature of about 175° to about225° C., in a water-immiscible, reaction-inert medium (the solvent has aboiling point of about 175° C. to about 225° C.) in the presence of amineral acid and preferably removing the water coproduct (e.g., bydistillation). Thus, this reaction is performed as a melt which obviatesthe removal of the water prior to crystallization required by priorprocesses which used aqueous solvent systems. The use of thewater-immiscible, reaction-inert medium described above (i.e., anon-solvent for the reactant and product) facilitates the removal andmeasurement of water coproduct (formed by the dehydration) as a means ofassessing the reaction's progress. This facilitates control of thereaction by reducing the amount of unreacted starting material andpolymeric condensation products that are not only difficult to removebut lead to decreased yields.

Preferable solvents include straight chain (C₁₀ -C₁₄) aliphatichydrocarbons, cyclic hydrocarbons such as cis- andtrans-decahydronaphthalene (or mixtures thereof i.e., Decalin®), andaromatic compounds such as p-cymene, 1,3,5-triethylbenzene,1,2,3,4-tetrahydronaphthalene (Tetralin®), and o-dichlorobenzene.Undecane is the most preferred solvent.

More preferably, 1,4-anhydro-DL-galactitol may be prepared by meltinggalactitol (m.p.188-191° C.) in refluxing undecane (b.p. 196° C.) in thepresence of a catalytic amount of a mineral acid, preferably phosphoricacid, and removing the resulting water formed by the dehydrationreaction. Preferably, the amount of acid is less than about 0.5 molewith respect to the galactitol. The resulting product may be purified bystandard practice such as recrystallization from, for example, propanol.

1,4-Anhydro-DL-galactitol may be separated into the corresponding D andL enantiomers on the basis of their physical chemical differences bymethods known per se, for example, by chromatography and/orderivatization followed by fractional crystallization.

The starting materials for the above described reactions are readilyavailable or can be easily synthesized by those skilled in the art usingconventional methods of organic synthesis.

Typical uses for the above described bulking agents include low caloriejellies, jams, preserves, marmalades, and fruit butters; dietetic frozenfood compositions including ice cream, ice milk, sherbet and water ices;baked goods such as cakes, cookies, breads, pastries and otherfoodstuffs containing wheat or other flour; confections (particularlychocolate compositions, chocolate centers, and fudge) and chewing gum;beverages such as soft drinks; sweet sauce, syrups, and toppings;icings; frostings and fillings for baked goods; whipped toppings;puddings; salad dressings; and as bulking agents for dry low caloriesweetener compositions containing cyclamate, saccharin, aspartame,alitame, stevioside, neohesperidin dihydrochalcone, or sucralose.

In the above described food compositions the bulking agents of thisinvention are combined with appropriate, readily available, foodingredients in suitable proportions according to methods consistent withthe standard skill in the art.

For example, the reduced calorie bulking agent replaces some, most, orall of the sugar normally in full calorie recipes, providing body andtextural properties to the food that would otherwise be lost. The actualamounts used vary depending on the level of caloric reduction desired,the specific low-calorie sweetener used, and the effects of the bulkingagent on processing characteristics, sweetness, flavor, and texturalproperties of the final food. A wide variety of food formulationsincorporate sugar, and thus would benefit by calorie reduction withappropriate use of this invention. Table 1, below, provides an exemplarylist of foods in which the bulking agents of this invention could beused.

The actual amount of bulking agent of this invention to be used variesgreatly depending on the food type, the kind and type of coingredients,the desired bulk physical properties (texture, viscosity, density,brittleness, etc.) and the selected flavor system of the finished food(e.g., strongly flavored foods such as chocolate frosting have beenshown to be acceptable with more than twice as much1,4-anhydro-D-glucitol as used in a bland vanilla frosting). In general,full calorie food examples cited in Table 1 or found in standard foodformularies (e.g., Food Products Formulary Series, AVI PublishingCompany Inc., Westport, Conn., Vol. 11 1975, Vol. IV 1982) or incookbook recipes can be simply modified by replacing some or all of thesugar with up to an equivalent amount of bulking agent and adjusting thelevel of low-calorie sweetener as appropriate to obtain the desiredsweetness and textural properties in the finished food. Final use levelsare then adjusted by those skilled in the art to yield an optimalbalance of flavor, texture, processing ease, and cost. Examples of howmuch sugar is commonly used in full calorie foods and, therefore, thepotential amount of bulking agent required for various foods follow:

                  TABLE 1                                                         ______________________________________                                                                        Typical Sugar Content (Range-Wt. %)           Food            Low                    High                                   ______________________________________                                        Peanut Brittle     58               88                                          Fondant                              58                 88                    Fudge Icing, white           56                 84                            Cookie filling, chocolate           51          77                            Marshallows                         46                68                      Chocolate Fudge                      42                 62                    Chocolate Icing                      41                 61                    Cream Filling                        33                 49                    Basic Icing                          30                 46                    Cookie Dough (refrigerated)          26                 40                    Bakers Jelly                         26                 38                    Pralines                             24                 36                    White Layer Cake                     22                  34                   Devil's Food Cake                    21                31                     Sugar Cookies                        19               29                      Brownies                             18                28                     Chocolate Chip Cookies               18               26                      Chocolate fudge topping              15               28                      Apple Jelly                         14                20                      Peanut Butter Cookies                13               19                      Danish Pastry                        13                19                     Ice Cream                            10                14                   ______________________________________                                    

As discussed above, in actual practice the amount of bulking agents ofthis invention that can be used will be equal to or less than the sugarlevels cited in Table 1. Additional guidelines for the preferred uses ofthe invention are discussed below.

The highly crystalline bulking agents of this invention are believed tomodify the glass transition temperature, melt profiles, viscosity andparticle size of semi-solid (including very viscous liquids or syrupsand gels) and solid foods and thus contribute to texture, mouthfeel andflavor impact. Thus, these bulking agents are particularly advantageousin high solids, high calorie foods such as fudge, cookie fillings, andfrostings.

The term "high solids" food refers to finished foods sufficientlylacking in free water that the subject bulking agent will be, in wholeor in part, in a solid crystalline state. The term "high calorie" foodspecifically refers to those foods in which either sugar or fat comprisea significant portion (e.g., greater than 10%) of the food solids.Hence, the preferred types of food particularly suitable for use of thecrystalline bulking agent of this invention are: crystallized sugarfoods consisting largely of sugar and flavorings such as hard candy;solid or semi-solid or aerated foods in which sugar syrups comprise thecontinuous phase and fats or other solids the discontinuous phase, e.g.,icings, sweet glazes, and fillings such as marzipan, toffees, caramels,fudges, fondants, filling creams, fruit syrups, jellies, marshmallows;and solid or semi-solid or aerated foods containing sugar in which fatis the continuous phase and sugar is the discontinuous phase e.g.,molded chocolates, chocolate coatings, nougats, truffles, wafer andbiscuit fillings, dairy butters and yogurt. Less easily classified butalso suitable are high solids baked goods (e.g., sugar cookies, date nutsquares, etc.) and frozen dairy desserts, where water, sugar, and/orbulking agent are crystallized to various degrees during the freezingprocess.

The general comments given above for generic substitution of bulkingagents for sugar apply in the preferred foods described above along withthe following more specific guidelines. Crystallized sugar foods such ashard candies generally contain very high sugar levels (e.g., greaterthan 50%) and therefore afford texture, flavor (e.g., sweetness), andmelt properties which preferably are not completely simulated byequivalent levels of bulking agent. In applications where sugar levelsexceed 50% of the finished food, maximum use level of the crystallinebulking agent is preferably limited to 25% of the finished food. Actualuse levels vary depending on the type, texture, melt and flavorrequirements of the finished food.

The second and third types of preferred foods described above oftenshare common ingredients (sugar or corn syrup, milk fat and/orconfectionery fats (e.g., cocoa butter, lauric fats, fractionated,interesterified and hydrogenated vegetable or tropical oils), water, andflavoring), but are processed differently to yield foods with differentratios of sugar to fat to air and different particle sizes. Componentratio and particle size distribution directly affect texture and meltprofile of the finished product. Particle size is generally controlledby carefully adjusting the rate of product cooling over a specifictemperature range and/or by one or more milling processes with rapidcooling and/or finer milling generally yielding food products withsmoother texture. Further processing details can be obtained fromnumerous sources such as lnglett's Fabrication of Foods, Vol. IV of theFood Product Formulary Series cited above.

Representative examples of foods incorporating the above-describedcrystalline bulking agents are included. While these examples set forthproportions of the crystalline bulking agents which are suitable for theparticular dietetic food involved, the quantities of crystalline bulkingagents required for other food compositions encompassed by thisinvention can be readily determined. Standard manufacturing proceduresare applicable to each of the recipes for dietetic foods which are givenin the examples.

It should be understood that the invention is not limited to theparticular embodiments described herein, but that various changes andmodifications may be made without departing from the spirit and scope ofthis novel concept as defined by the claims.

EXAMPLE 1 Thousand Island Dressing Total weight 100 Grams.

    ______________________________________                                        Ingredients                 Percent                                           ______________________________________                                         WaterA (for xanthan and alginate hydration)                                                              6.00                                                Xanthan gum (Keltrol F).sup.1                                      0.15       Propylene glycol alginate (Kelcoloid LVF).sup.1                    0.15       Modified food starch (Ultra-Tex 4).sup.2                           2.50       1,4-anhydro-D-glucitol                                            6.00                                   Maltrin M-200 (corn syrup solids).sup.3                                                            4.00                          Salt                                                              1.50                                   Sugar                                                                                             15.00                          Seasoning blend (Wisconsin Spice, Pfizer Inc, low fat type).sup.4                                       2.00                                                Titanium dioxide.sup.5                                                                                  0.10                                                Potassium sorbate                                                  0.10       Sodium benzoate                                                    0.10       Monosodium glutamate                                               0.15       Vinegar (50 grain white distilled)                                16.00       Tomato paste (hot break)                                           5.00       Veltol® (1% w/w H.sub.2 O).sup.4                             0.50                                    Pickle relish (sweet)                                                                              5.50                          FD&C yellow #5 (0.10% w/w H.sub.2 O).sup.5                     0.15                                      FD&C yellow #6 (1.0% w/w H.sub.2 O).sup.5                                                      0.01                              Egg yolks (frozen 10% salt).sup.6                                                                       2.00                                                Soybean oil                                                        9.25       Polysorbate 60.sup.7                                                                                    0.10                                                Water B                                                  23.74                TOTAL                                                                       ______________________________________                                                                    100.00                                             .sup.1 Kelco                                                                  .sup.2 National Starch and Chemical Corporation                               .sup.3 Grain Processing Corporation                                           .sup.4 Wisconsin Spice, Inc.                                                  .sup.5 Warner Jenkinson Company                                               .sup.6 Egg Corporation of America                                             .sup.7 ICI Chemical Corporation                                          

Xanthan gum and alginate were prehydrated in water A for 15 minutes withoccasional stirring. Water B was added to the mixer. The dryingredients, except for the pickle relish, were added. The mixture wassheared for two minutes. The sides were scraped and the mixture wassheared for two more minutes. The mixture was homogenized using acolloid mill (i.e., Greerco Model W250) and the pickle relish wasstirred in after milling. A Cuisinart food processing center with a 1 kgbatch size was used to mix the ingredients.

EXAMPLE 2 Vanilla Frosting Total Weight 100 Grams

    ______________________________________                                        Ingredients          Percent                                                  ______________________________________                                           Sugar, 10X                                             61.57                 1,4-anhydro-D-glucitol                             8.71                       Powdered non-fat dry milk                          8.59                       Solka-Floc 900.sup.1                                1.00                      Vegetable shortening (Creamtex).sup.2               4.50                      Dur-Em 114.sup.2                                    4.50                      Water                                              9.36                       Avicel RC 591 F.sup.3                               0.77                      Vanilla extract                         1.00                                  TOTAL                                            100.00                     ______________________________________                                         .sup.1 Fiber Sales & Development Corp.                                        .sup.2 Van Den Bergh                                                          .sup.3 FMC                                                               

The sugar, 1,4-anhydro-D-glucitol, powdered non-fat dry milk andSolka-Floc 900 were blended and mixed for 3 minutes at speed 1 in aKitchenAid mixer (Model K5SS). The vegetable shortening and Dur-Em 114were added to the mixture and mixed for 3 minutes at speed 1. The sidesof the mixer were scraped down and the mixture was mixed for 1 minute atspeed 2. The Avicel RC 591F was added to the water slowly and mixed withan overhead stirrer with increasing speed as the Avicel was added. TheAvicel solution was added to the first mixture and mixed on speed 2until a frosting was formed, followed by additional mixing for 2 minutesat speed 4. The vanilla extract was added to the mixture with subsequentmixing for 1 minute at speed 4. The sides of the mixture were scrapeddown followed by additional mixing for 30 seconds at speed 4.

EXAMPLE 3 Chocolate Frosting Total Weight 100 Grams

    ______________________________________                                        Ingredients         Percent                                                   ______________________________________                                            Vegetable shortening (Creamtex).sup.1                                                            6.00                                                     Dur-Em 114.sup.1                                     1.90                     Polysorbate 60.sup.2                                 0.10                     Sugar, powdered                                    41.00                      1,4-anhydro-D-glucitol                             26.00                      Avicel, PH-101.sup.3                                 4.00                     Cocoa powder, D-11-SB.sup.4                          2.70                     Chocolate Flavor                                    0.30                      Salt                                                0.25                      Ultratex 4.sup.1                                     0.80                     Aspartame.sup.6                                      0.15                     Veltol®                                       100 ppm                     Water                                              15.40                      Pectin.sup.8                                         0.75                     Vanilla extract 1X (#29 pure k).sup.8           0.65                          TOTAL                                             100.00                    ______________________________________                                         .sup.1 Van Den Bergh                                                          .sup.2 Tweeg, Inc.                                                            .sup.3 FMC Corporation                                                        .sup.4 De Zaan, Inc.                                                          .sup.5 Tastemaker, #264907                                                    .sup.6 NutraSweet                                                             .sup.7 Hercules, BB Rapid Set                                                 .sup.8 Virginia Dare                                                     

The vegetable shortening, Dur-Em 114 and polysorbate 60 were combinedand melted. The powdered sugar, 1,4-anhydro-D-glucitol, Avicel, cocoapowder, chocolate flavor, salt, Ultratex, aspartame and veltol werecombined and added to the first mixture. The combined mixture wasblended evenly in a KitchenAid electric mixer (Model K5SS) on low speedfor two minutes. The dry ingredients were sifted as necessary if therewas lumping. The pectin was added slowly to water and the vanilla wasstirred in to the pectin water solution. The pectin vanilla mixture wasadded to the dry ingredients and the combined mixture was mixed on lowspeed until the ingredients were moist followed by mixing for 4 minutesat a speed of 6 to 8.

EXAMPLE 4 Chocolate Syrup Total Weight 100 Grams

    ______________________________________                                        Ingredients             Percent                                               ______________________________________                                        Cocoa, Dutched.sup.1 (10-12% fat)                                                                     10.00                                                   Salt                                                       0.07                                      Vanillin                                                                               0.05                                          Xanthan gum                                                0.05                                      1,4-anhydro-D-glucitol                                                                34.98                                          High fructose corn syrup.sup.2                             31.98                                     Water                                                                                 22.85                                          Aspartame                                                  0.025                                     TOTAL                                                                                100.00                                        ______________________________________                                         .sup.1 De Zaan type D11-V                                                     .sup.2 American Maize Products Co.  TruSweet 42                          

The cocoa, salt, vanilla and xanthan gum were blended together. The1,4-anhydro-D-glucitol, high fructose corn syrup and water were mixed.The two mixtures were combined and aspartame was added followed bymixing until the mixture was smooth and homogeneous with a labdispersator.

EXAMPLE 5 1,4-Anhydro-D-Glucitol

The procedure below was based very closely on the preparation of K.Bock, C. Pedersen, and H. Thogersen (Acta Chem. Scand Ser. B, 35, (1981)441-449.)

D-Glucitol (Aldrich, 1150 g, 6.31 mol) was suspended in aqueous 3M H₂SO4 (550 mL) and heated at reflux with stirring under N₂ overnight. Thedark brown solution was cooled and neutralized using Amberlite® IRA-93resin (OH-, ˜4 L) Rohm and Haas, (Phil., Pa.). The resin was removed byfiltration; the filtrate was decolorized using activated carbon (4 g)which was subsequently removed by filtration.

Water was evaporated from the solution using a rotary evaporator (bathtemp =80° C.). Absolute ethanol (1 L) was added; gentle warming wasrequired to dissolve the colorless, viscous residue. The solvent wasremoved under aspirator pressure (bath temp =60° C.) which effectedcrystal formation. Additional ethanol (1.5 L) was added; thesolid-liquid mixture was concentrated under aspirator pressure until noadditional distillate was obtained.

The residue was dissolved in absolute ethanol (1.5 L) and heated toeffect dissolution. The mixture was cooled slightly, seeded, and stirredovernight at ambient temperature. The mixture was then cooled to 0 ° C.and vacuum filtered using a Buchner funnel. Solids were re-pulped inabsolute ethanol (0.5 L, -5° C.) then re-filtered and rinsed withadditional cold ethanol (0.5 L).

Solids were dried on a Buchner funnel under N₂, then ground (mortar andpestle) and dried on the rotary evaporator (high vacuum, 60° C. bath)for 4 hours. The final weight of the 1,4-anhydro-D-glucitol was 459 g(44.3%). HPLC indicated that the major impurity was residual sorbitol,˜0.8%). Solids melted between 113 and 114.5° C.; a doubly recrystallizedsample melted between 114 and 115° C. and exhibited a rotation of -22.9°[c=5.4, H₂ O, lit=-22.4° at the same concentration, see Bock et al.).

The above preparation was alternately performed using both Duolite®A-192L and Amberlite® IRA 400 (both OH-) Rohm and Haas (Phil., Pa.) asneutralization resins and n-butanol and 2-propanol as recrystallizationsolvents.

EXAMPLE 6 1,4-Anhydro-DL-Galactitol

Galactitol (Aldrich, 40 g, 220 mmol) was suspended in undecane (200 mL),acidified with H₃ PO₄ (50 mL, 0.4 mmol), and heated to reflux under N₂.Water (4.4 mL, 244 mmol, 1.1 equiv) was collected in a Dean-Stark trapover 1 hour. The reaction was cooled and the undecane decanted. Theresulting dark syrup was rinsed with hexane and dried under a stream ofN₂.

A small portion of the crude syrup was partially dissolved in refluxingacetonitrile. The resulting mixture was slowly cooled to ambienttemperature and left undisturbed overnight. Fine needles were collectedfrom the sides of the flask for use as seed crystals.

The remaining crude syrup was dissolved in 1-propanol (100 mL), treatedwith Darco® KB-B activated carbon (2 g), and heated to reflux for 1 h.Upon cooling to ambient temperature, the mixture was filtered through aCelite® pad and the filtrate concentrated in vacuo to a weight of 100 g.The solution was seeded, then stirred at ambient temperature overnight.The resulting crystal-containing mixture was cooled to -4° C. over 8hours then stirred an additional 24 hours at this temperature. Crystalswere isolated by vacuum filtration. The resulting filter cake was rinsedwith cold 1-propanol (50 mL); additional washing was performed withether (100 mL) and pentane (100 mL) to aid in the removal of residualalcohol.

Drying under high vacuum yielded 1,4-anhydro-DL-galactitol (22.3 g,61.9%); mp 69.5-71° C.; TGA (1% loss at 209° C.); ms calc'd (M+H)165.0759 (obs'd 165.0764); IR (KBr) 3290, 2994, 2960, 2861, 1354, 1210,1132, 1088, 1068, 986, 917, 876, 742, and 505 cm⁻¹. ¹ H NMR: δ3.59 (dd,1 H, J_(6a),6b 11.8, J₅,6b 7.3, H-6b), 3.68 (dd, 1 H, J₅,6a 4.3, H-6a),3.71 (app-t, 1 H,J₃.4 =J₄,5 4.8, H-4), 3.81, (m, 2 H, H-1b, H-5), 3.97(dd, 1 H, J_(1a),1b 10.1, J_(1a),2 4.7, H-1a), 4.10 (ddd, 1 H, J₂,3 2.7,J₃,5 0.9 Hz, H-3), 4.21 (d app-t, 1 H, H-2). The structure wasadditionally confirmed by X-ray crystallography.

The above preparation was also performed using Tetralin® as analternative solvent and with methanesulfonic acid and toluenesulfonicacid as alternate acid catalysts. The above preparation was alsoperformed using cellosolve, ethanol, dimethoxyethane, 2-propanol,ethanol/methyl tert-butyl ether, n-butanol, dioxane, and acetonitrile asalternative recrystallization solvents.

What is claimed is:
 1. A food product containing a low calorie bulkingagent comprising:a. 1,4 anhydroglucitol or 1,4-anhydrogalactitol; and b.a food ingredient.
 2. The food product as recited in claim 1 whereinsaid low calorie bulking agent is 1,4 anhydro-DL-glucitol.
 3. The foodproduct as recited in claim 2 wherein said low calorie bulking agent is1,4 anhydro-D-glucitol.
 4. The food product as recited in claim 3wherein said food product is a high calorie, high solids, food product.5. The food product as recited in claim 4 wherein said food product is abaked good.
 6. The food product as recited in claim 4 wherein said foodproduct is a confection.
 7. The food product as recited in claim 4wherein said food product is a frozen dessert.
 8. The food product asrecited in claim 4 wherein said food product is a chewing gum.
 9. Thefood product as recited in claim 4 wherein said food product is a bakedgoods frosting or a baked goods filling.
 10. The food product as recitedin claim 2 wherein said low calorie bulking agent is 1,4anhydro-L-glucitol.
 11. The food product as recited in claim 1 whereinsaid low calorie bulking agent is 1,4-anhydro-DL-galactitol.
 12. Thefood product as recited in claim 11 wherein said low calorie bulkingagent is 1,4-anhydro-D-galactitol.
 13. The food product as recited inclaim 11 wherein said low calorie bulking agent is1,4-anhydro-L-galactitol.
 14. The food product as recited in claim 11wherein said food product is a high calorie, high solids, food product.15. The food product as recited in claim 14 wherein said food product isa baked good.
 16. The food product as recited in claim 14 wherein saidfood product is a confection.
 17. The food product as recited in claim14 wherein said food product is a frozen dessert.
 18. The food productas recited in claim 14 wherein said food product is a chewing gum. 19.The food product as recited in claim 14 wherein said food product is abaked goods frosting or a baked goods filling.
 20. A method of preparing1,4-anhydro-DL-galactitol comprising:heating galactitol in awater-immiscible, reaction-inert medium that has a boiling point ofabout 175° C. to 225° C. in the presence of a mineral acid.
 21. Themethod as recited in claim 20 wherein said mineral acid is phosphoricacid and said medium is undecane.
 22. The method as recited in claim 21wherein said galactitol is refluxed in said undecane and water isremoved.